NL8000765A - NEW BENZAMIDINE DERIVATIVES, METHOD FOR PREPARING THESE COMPOUNDS AND FUNGICIDE PREPARATIONS CONTAINING THE COMPOUNDS, - Google Patents

Description

i 1 49 513 / Bos / AS - 1 -

Novel benzamidine derivatives, process for the preparation of these compounds as well as fungicidal compositions containing the compounds.

The invention relates to a new group of benzamidine derivatives, to a process for their preparation and also to a new use of these benzamidine derivatives as an agricultural fungicide.

Conventionally, various kinds of organocurvic compounds, arbene compounds, copper compounds and the like have often been used for agricultural fungicides. However, these compounds have been found to have serious drawbacks such as residual | 10 soil contamination and toxicity or residual toxicity to humans and animals, limiting its use. Furthermore, drug-resistant fungi or bacteria have recently appeared in plant diseases of various field crops, particularly powdery mildew, gray mold, blast disease and sclerotium disease.

Therefore, the effect on such plant diseases of chemicals that have been used for many years has diminished.

For the above reasons, it is desirable to develop a new type of agricultural fungicides.

As a result of extensive studies on the fungicidal effect of different compounds, the applicant has found a new group of compounds that are novel in themselves and which have an excellent fungicidal effect against various plant diseases.

An object of the invention is to provide new benzamidine derivatives.

Another object of the invention is to provide a new process for the preparation of these benzamidine derivatives.

A further object of the invention is to provide an agricultural fungicidal composition containing one or more of these benzamidine derivatives as the active ingredient.

800 0 7 65 - 2 -

The new compounds of the invention are compounds from the benzamidine group represented by formula 1 of the formula sheet, wherein X represents a lower alkyl group, a halogen atom or a methoxy or 5-dimethylamino group, n represents 0, 1, 2 or 3, 1 2 R and R may be the same or different and each represent an alkyl, alkenyl, cycloalkyl or phenyl group or, together with the nitrogen atom to which they are attached, may form a saturated 5-7 membered alicyclic group which may be an oxygen atom as a member of the ring adjacent to the nitrogen atom and which may be substituted with one or two methyl groups, and 3 R represents a hydrogen atom or a straight or branched chain alkyl, alkenyl or alkynyl group, a chlorine or non-chlorine substituted benzyl group, a cyano, cyanoalkyl, alkoxycarbonylmethyl, Qt-alkoxycarbonylethyl, alkoxymethyl or bis (alkoxycarbonyl) methyl group, a phenoxyethyl group or a sub-alkyl or alkoxy group phenoxyethyl group, a formula 2 formula (in which represents a hydrogen atom or a lower alkyl group, a halogen-substituted methyl group, a lower alkoxy, lower alkoxyalkyl, lower alkenyl, lower alkylthiomethyl-furyl, thienyl - lower alkylthio or phenylthiomethyl group, a phenoxy group, whether or not substituted by a methyl group, or a phenyl group, whether or not substituted by a halogen atom or a methyl, methoxy or nitro group), a group of the formula III of the formula sheet 6 (wherein R and R may be the same or different and each represents a hydrogen atom or a lower alkyl or cyclohexyl group, an anilinocarbonyl group, whether or not halogen substituted, or a phenyl group whether or not substituted by a halogen atom or a methyl group), a group of formula 4 of the formula-35 sheet (wherein R represents a lower alkyl, cyclohexyl, benzyl, lower alkoxycarbonyl or phenoxycarbonyl group), 8 o f a group of the formula -SC ^ -R (where R is a lower alkyl, trifluoromethyl or chloromethyl group or a halogen or methyl group 800 0 7 65 or not

I

- substituted phenyl group), or a salt thereof represented by the formula 5 of the 12 3 formula sheet, wherein X, n, R, R and R have the same meanings as defined above, Y represents an acid 5 and m represents the is the value required to form the salt with Y.

As the lower alkyl group represented by X, a lower alkyl group having one or two carbon atoms such as the methyl and ethyl group can be mentioned, for example.

As the alkyl group represented by R or R, mention may be made, for example, of an alkyl group having 1 to 5 carbon atoms, such as the methyl, ethyl, propyl, butyl and pentyl group.

1 2

As the alkenyl group 15 represented by R or R, for example, an alkenyl group having 3 or 4 carbon atoms such as the allyl and 2-butenyl groups can be mentioned.

12

As the cycloalkyl group represented by R or R, there may be mentioned, for example, a cycloalkyl group having 5 or 6 carbon atoms, such as the cyclopentyl and cyclo-20 hexyl group.

For example, as the saturated 5-7 membered alicyclic group formed by co-operation of R and R together with the nitrogen atom to which they are attached, mention may be made of the 1-pyrrolidinyl, 1-pipe-ridyl, 2- methyl-1-piperidyl, 2,6-dimethyl-1-piperidyl and hexahydroazepinyl group.

3

As the straight or branched chain alkyl group represented by R, there may be mentioned, for example, an alkyl group having 1 to 13 carbon atoms, such as the methyl, ethyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and tridecyl group.

3

As the straight or branched alkenyl group represented by R, an alkenyl group having 3 or 4 carbon atoms such as the allyl and 2-butenyl group can be mentioned, for example.

3

As the straight or branched chain alkynyl group represented by R, there may be mentioned, for example, an alkynyl group having 3 or 4 carbon atoms, such as the allyl and 800 0 7 65 P τ - 4 - 2-butenyl group.

3

As the straight or branched chain alkynyl group represented by R, an alkynyl group having 3 or 4 carbon atoms, such as the propargyl-5 and butynyl group, may be mentioned, for example.

3

As the benzyl group substituted by chlorine represented by R, mention may be made, for example, of the chlorobenzyl and dichlorobenzyl group; as the cyanoalkyl group represented by R, there may be mentioned, for example, a cyanoalkyl group having 2 or 3 carbon atoms, such as the cyanomethyl and cyanoethyl group.

3

As the alkoxycarbonylmethyl group represented by R, there may be mentioned, for example, an alkoxycarbonyl group having 3-6 carbon atoms, such as the methoxycarbonyl-15 methyl, ethoxycarbonylmethyl, isopropoxycarbonylmethyl, n-propoxycarbonylmethyl and butoxycarbonylmethyl group.

3

As the't'-alkoxycarbonyl-ethyl group represented by R, mention can be made, for example, of a <x -alkoxy-20-carbonylethyl group with 4-6 carbon atoms, such as the cc-methoxycarbonylethyl, cc-ethoxycarbonylethyl, (X-isopropoxycarbonylethyl, an-propoxycarbonylethyl) and oc-butoxycarbonylethyl group.

3

As the alkoxymethyl group represented by R, there can be mentioned, for example, an alkoxymethyl group with 2-5 carbon atoms, such as the methoxymethyl, ethoxy-methyl, propoxymethyl and butoxymethyl group.

3

As the bis (alkoxycarbonyl) -methyl group represented by R, there may be mentioned, for example, a bis (al-30-koxycarbonyl) methyl group with 5-11 carbon atoms, such as the bis (methoxycarbonyl) methyl, bis (ethoxycarbonyl) -methyl, bis (propoxycarbonyl ) methyl and bis (butoxycarbonyl) methyl group.

3

As the substituted phenoxyethyl group represented by R, mention can be made, for example, of a phenoxyethyl group having 9 or 10 carbon atoms, such as the methylphenoxyethyl, ethylphenoxyethyl, methoxyphenoxyethyl and ethoxyphenoxyethyl group.

3

As the group with the 800 0 7 65 * * - 5 - formula 2 also represented by R, mention can be made, for example, of a formyl group, a lower alkanoyl group with 2-4 carbon atoms, such as an acetyl, propionyl, n-butyryl- and isobutyryl group, a halogen-substituted acetyl group, such as the chloroacetyl, dichloroacetyl, trichloroacetyl, bromoacetyl and iodoacetyl group, a lower alkoxycarbonyl group with 2-5 carbon atoms, such as the methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl -, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycar-10 bonyl, sec.butoxycarbonyl and tert.butoxycarbonyl group, a lower alkoxyalkanoyl group having 3-5 carbon atoms, such as the methoxymethylcarbonyl, ethoxymethylcarbonyl and ethoxyethylcarbonyl group having a lower alkenoyl 5 carbon atoms, such as the acryiloyL, crotonyl, metha-15-cryloyl, 3,3-dimethylacryloyl and tert. 2,3-dimethyl-acryloyl group, a lower alkylthiomethylcarbonyl group having 3-6 carbon atoms, such as the methylthioacetyl, ethyl 1-thioacetyl, propylthioacetyl, isopropylthioacetyl and butylthioacetyl group, a furoyl group, a thenoyl group, a lower alkylthiocarbonyl group with "2-5 carbon atoms, such as the methylthiocarbonyl, ethylthiocarbonyl-butylocarbonyl, isylcarbonyl, isyl a phenylthiomethylcarbonyl group, a phenoxycarbonyl group, a halophenylcarbonyl group, such as the p-chlorophenylcarbonyl and 2,4-dichlorophenylcarbonyl group, a methylphenylcarbonyl group, a methoxyphenylcarbonyl group and a nitrophenylcarbonyl group.

3

As the group of formula 3 also represented by R, mention can be made, for example, of a carbamoyl-30 group, a lower alkyl carbamoyl group with 2-5 carbon atoms, such as the methyl carbamoyl, ethyl carbamoyl, n-propyl carbamoyl, isopropyl carbamoyl, n- butylcarbamoyl, isobutylcarbamoyl, sec.butylcarbamoyl and tert.-butylcarbamoyl, a di-lower alkylcarbamoyl group having 3 to 9 carbon atoms, such as the di-methylcarbamoyl, diethylcarbamoyl, di-n-propylcarbamoyl -isopropyl-carbamoyl-, di-n-butylcarbamoyl-, di-isobutylcarbamoyl-, di-sec.butylcarbamoyl-, di-tert-butylcarbamoyl- and cyclohexylcarbamoyl-anhalo-carbonyl-anyl-anylcarboxylic group, 80 0 0 7 65 -carbonylcarbamoyl group, such as the 4-chloroanilinocarbonyl-carbamoyl group, a phenylcarbamoyl group, a halophenylcarbamoyl group, such as the 2-chlorophenylcarbamoyl and 3,4-dichlorophenylcarbamoyl group and a methylphenylcarbamoyl group.

3

As the group of formula 4 also represented by R, mention can be made, for example, of a lower alkylthiocarbamoyl group with 2-5 carbon atoms, such as the methylthiocarbamoyl and ethylthiocarbamoyl group, a cyclohexylthiocarbamoyl group, a benzylthiocarbamoyl group such as a lower alkoxycarbonylthi group, 3-alkoxycarbonylthi group the methoxycarbonylthiocarbamoyl, ethoxycarbonylthiocarbamoyl, n-propoxycarbonyl-15 thiocarbamoyl, isopropoxycarbonylthiocarbamoyl, n-butoxycarbonylthiocarbamoyl, isobutoxycarbonylthio-carbamoyl, sec. butoxycarbonylthiocarbamoyl group and a phenoxycarbonyl thiocarbamoyl group.

3 20 If the group also proposed by R with the

O

formula -SC ^ R can be mentioned, for example, a lower alkanesulfonyl group with 1 or 2 carbon atoms, such as the methanesulfonyl and ethanesulfonyl group, a trifluoromethanesulfonyl group, a chloromethanesulfonyl group, a benzenesulfonyl group, a halobenzenesulfonyl group, such as the 4-chlorobenzenesulfonyl, such as the 4-chlorobenzenesulfonyl bromobenzene sulfonyl and 2,5-dichlorobenzene sulfonyl group and a toluenesulfonyl group.

Examples of compounds of the invention are listed in Table A.

Table A, 80 0 0 7 65 * r - 7 -

TABLE A

ref Substituents in the formula 5 Physical bond "eigenschappen properties

No. η'γΤγ_ R1 R2 R3 (Y) m

> o- 'Λ = * «*“ "": "S

(86 ° C / 3mmHg) k. p.

2 ”n-C-, Η n-C.H_" "95-98 ° C / 3nunHg k.p.

3 "n-C.H n-C H" "117-119 ° C / 3mmHg 4" "^ cL" "98-101 ° C / ^ 4 3mmHg O k.p.

"" 111-112 ° C / 3mmHg / \ k * P6 "Λ J" "141-14 7 ° C / '-' 4mmHg / - \ k.p.

7 "-NO" "145-146 ° C / N - 6mmHg k. P.

8 "CH JT \" 135-137 ° C / 3 \ = / 4mmHg 'Mp. 83-85 ° C) 800 0 7 65

continued Table A

η ^ τγ_ R1 R2 R3 (Y) m 4 - 8 -

ÖCH3 k P

CH3 CH3 H none 65-68 ° C / 4mmHg k. p.

10 "C ~ H, C-H-" "97-106 ° C / 4mmHg K p.

11 "n-C, H7 n-C3H." "105-107 ° C / 3mmHg

12 "i-C3H7 i ~ C3H7" "Srt> P-71-73 ° C

k. p.

13 "n-C.Hg n-C.Hg" "137-140 ° C / 3mmHg k. P.

14 "i ~ C * Hg i-C.Hq" "118-122 ° C /

ImmHg k. p.

15 "n-C-H. I n-Cj-H,." "150-155 ° C / 3mmHg k. P.

16 "i-C ^ H ,, i-cqHn" "130-134 ° C /

ImmHg k. p.

17 "n-C, H7 n-Cj-H ,," "129-134 ° C / 2mmHg 18 ~ (j ^)" "% 2 1i5430 800 0 7 65

Continued Table A

X "^ 0_ R1 R2 R3 (Y) m

a

- 9 - _ / CH3 - k.p.

19 A. n_C6H13 n "C6H13 H none 156-16 3 ° C / \ - / ImmHg 20" n-C8H17 n_C8H17 "" nD2 1 »4970 Λ ^ | k * P · 21” -N J "" 119-121eC /

Pk. p.

129-134 ° C / 3mmHg un3 CH3 v ~ Ί / \ sn.p.

23 · "" "61-63 ° C

ch3 / CH ^ 24 V ~ \ - n-C-H- n-C ^ H "" 117-119 ° 0 / \ = / 4mmHg 25 CH, - / "V · C-Ης C9H" "105-108 ° C / ^ 4mmHg k.p.

26 "n-C-H- n-C H" "115-122 ° C / 2mmHg / rC3 k.p.

27 \ r ~ "" "" 117-120 ° C / CH / ImmHg k.p.

28 "n-C.Η- n-C.Hg" "130-134 ° C /

ImmHg 80 0 0 7 65

continued Table A

ΧηγΑ- I R ^ R2 R3 (Y) m - 10 - / ri. kp · 29 \ _ / i-C5Hll i_C5Hll H none 145-150 ° C / CH lmmHg "Λ" 30 KV nC-> H7 nC-jH7 "" 113-119eC / ^ = <CH 2mmHg ΊΛ 31 CH3- ^ J- n-C4Hg n-C4Hg "" n * 4 1.5160 __ ^ CH3______ 32 nC-H7 nC-H_ "" 114-117 ° C /

Nc = Xr „lmmHg __L2n5_____ k. p.

33 "i" C5HH i'C5Hll "" 139-143 ° C / lmmHg 34 fy ”" "" m-iis ^ c / N = ^ 2mmHg k · p · 35 "n-C3H7 nC, H7" "124-130 ° C / lmmHg k. p.

36 "nC.Hq nC.Hq" "132-143 ° C / lmmHg CH3 ° k 37 Q- n-c3H7 n-c3H7"; P; c / lmHg 38 CH30 O] C2H5 C2H5 "" 123-126 ° C / 80 0 0 7 65% * «·

continued Table A

^ JR ^ R2 R3 (Y) m - 11 - 39 nC ^ H7 nC..H7 H none 134-139 ° C / 3 X ^ = / J 2mmHg CH3 ° \ ”40 CH ^ O-fV" "" "134 -149 ° C / 3 X '= / InunHg kp

41 '"ί - <: 5Ηΐΐ i" C5Hll "" 167-170eC /

ImmHg; ~ 42 \ r ~ CHi CH- ”" 129-134 ° C / 3 lOmmHg k.p.

43 "C-H. C-Ης" "99-103 ° C /

ImmHg k. p.

44 "n-C, H7 n-C, H?" "123-126 ° C /

ImmHg k. p.

45 "n-C.Hg n-C.Hg" "138-144 ° C /

ImmHg cl 46 A- C-H- C7 Ης "" 114-120 ° C / N = / 3mmHg k. p.

47 "n-C.Hg n-C.Hg" "141-143 ° C /

ImmHg 48 ΰ7Ης C-H- "" 112-1170C /. 3mmHg snη n 7 β * 5 * - 12 -

continued Table A

Xnv ^ y_ R1 R2 R3 (Y) m 49 n-C3H7 n-C3H? H no 127-133 ° C / = 1mmHg cl 50 C2H5 C2H5 "" 123-129 ° C / k. p.

51 '"n-C, H7 n-C, H?" "135-143eC / J 2mmHg cl V-τΛ k.p.

52 Cl-V V C-Ης C7H- "" 138-147 ° C / V = / 5 3mmHg cl 53 kV "" "" 130-136 ° C / J> - '2mmHg __Cl_______ k.p.

54 "n-C, H-, n-C1H7" "127-134 ° C / J 2mmHg cl" 55 fy-C7Hc C7H, "" 122-127 ° C / N = <2mmHg __Cl______ k. O.

56 "n-C3H7 n-C7H7" "130-135 ° C / mmHg

Br 57 f \ - C-, Η- C-H, "" 115-120 ° C / \ = / "3 2mmHg 58" "" "105-108 ° C / ==. 6mmHg 800 0 7 65, - 13 -

continued Table A

R1 r2 r3 (Y) m 59 F ^ y C2H5 C2H5 H none ^ -12TC / CH3! ^ fill \ lT \ "" "" 146-153 ° C / / \ = / 3mmHg ch3__ C1 'τ- ^ Λ- "" "" 138-146 ° C / 61 \ = / 2mmHg ---- «Ö- -c ^ nc ^ "" «= 2¾ CA '"

64 O- "" "HCl 14 3-14 6 ° G

65 "" "" HBr ^ 65-169 ° C

66 "" "" HI 177-178 ° C

67 "" "" HNO 3 95-97 ° C

68 ........ hCW4 Ti3-146 «C

flOO 0 7 65 * - 14 -

continued Table A

Χη · Ί0- R1 R2 R3 (Y) m

69 C2H5 C2H5 H HCOOH

33 ...... [COOHCH (OH)] 2SJjP: i69.c

71 "" "(COOK), SiO: 130, C

33 "...... CH2 (COOH) 2 ^ 100C

^ COOH

7-3 11 11 11 11 (CU ΐ STfl. P.

2 4 \ θΟΗ 113-121'C

74 (h) -cooh ^ Ρ · 3ί (, 75 "" "" COOH ^ -P-

10 / 107-109 ° C

. __ 76 C> C00H "iP: U9.c OCOCHj 77 Q-cooh ®iP: 120.c

78 "....... IOOC" 0-COOH1Ó2 :: 03 "C

80 0 0 7 65 - 15 -

continued Table A

Xn ^ R1 R2 R3 (Y) m «79 c2h5 h Os ° 3H i3i" i32 ° c

--- 1- NO

_ 80 "" "" hoO-N ° 2 Ξΐ58-160 ° α _______ _ rt sm «p ·

81 'n-C3H? N-C3H7 "HC5. 181-185 ° C

-CH2CH = -CH2CH = m „sm.p.

82 "Ch2 CH2 137-141eC

83 "n-C4H9 n-C4Hg" "169-171eC

84 CH, C 2 H 5 C 2 H 5 "205-207 ° C

CH ^ "

85 CH 3 CH 3 "5 ^ 3-254 ° C

86 "" "267-268 ° C

_

87 ^ 3 "" ^ ° ^ 7 n ~ C ^ 7 "" 171-172 ° C

83 C2H3 C2H5 "" 232-23 3 ° C

fiili) Π 7 fi *?

continued Table A

R1 R2 R3 (Y) rn - 16 -

89 Q- “) Ό '” Ct ^ 34-235 ° C

90 CH3O-O-C2H5 C2H5 HCl-xHjO

91 'O "" "CH3CH2COOH n ^ 1 !, 5190 .CH ^ COOH ..

92 "" "" 0? 1 η „1.5330

nch2cooh U

93 "" "" CH 2 = CHCOOH n31l, 5443

aCOOH

3Π. p.

190 ° C

____II_COOH__

^ COOH

95 "" "" Γ JT n23l, 5645

96 ........ CH3-0-S ° 3H ^ 24: 26 »C

97 "" "" -ΐ2Η25θ · 503Η n25l, 5211 CIUCOOH l * · tc 98 "" "" HO-C-COOH n "1.5104 I D 1 ch2cooh 800 0 7 65 * - 17 -

continued Table A

Χ »φ R1 R2 R3 (*)" »

99 / ~ V C2H5 C2H5 H Q-SO3H 224-226 ° C

oh C0CH ^ 100 ........ JCL nDSl '5452 ____Ch__ f »t * ^ in · p ·

101 "" "CH3 HI 139-142 ° C

,, 3ΓΠ. p.

102 "" "C2H5 155-153 ° C

103 "" "n-C3H?” 122-124 ° C

k ·. p.

104 "" "i-C3H7 phene 98-104 ° C / 5mmHg

105 "" "n_C4H9 HI 109-111 ° C

k. p.

106 "" "rv — C c-H 1, no 128-132 ° C / 5 11 5mmHg ^ · Ρ · 107" "" £ U-r \ 7-Cl "17 2-177 ° C / Y Ns = / LnunHg K.p.

108 ...... i-CrH, 1 "126-133 ° C / D 11 6mmHg 80 0 0 7 65

R1 R2 R3 (Y) m - 18 -

continued Table A

109 Q- C2H5 C2H5 ch3 “^^“ KCl ^ 54-156 ° C

k. p.

110 "" "-CH-COOC-Hb no 130-137 ° C / 3mmHg k. P.

111 "" "-CH2CH2CN" 161-165 ° C / 7mmHg COOC-, Ης ..

11T "" "^ tj / t-D II

112 "l-H \ D 1 5023 COOCtH5 u k. P.

113 "" "- (CH7) 10'CH-" 159 ° C / 0.45mmHg k. p.

114 "" "- (CH2) n-CH," 155-159 ° C / l 0.25mmHg k. p.

115 "" "- (CH2), 2-CH" 164-169 ° C / 0.25mmHg k. P.

116 "" "CH2CH20-fVCH1" 156-161 ° C / 0.25mmHg _ k · P · 117 "-CH2CH20- ^)" 152-155 ° C / 0.25mmHg

. öcTTTZ

V ^ v k.p.

118 "" "-CH0CH20-V_)" 164-171 ° C / 0.35mmHg 80 0 0 7 65 * -19-

continued Table A

R1 R2 R3 (ï) m 113 Q. C2H5 C2 «5 -CH2CN seen Ï & 1 £ C / 120 .....- CH OCH" 6mmHg 4i sin * p *

121 "" "CN 84-85 ° C

CH ^

122 pounds 5 ^ 3H7 = 3H7 CH3 HI

21 j_23 "" "" no nQ 1.5152 124 ...... C2H5 "n21 1.5290

125 "" "n ~ C3H7 HI 158-159 ° C

226 "" "" none n2 ^ 1.5054 n n- n-,. ut sm.p.

127 C4H9 C4H3 131-133 »C

128 "C3H7 C3H7 n'CA" = 89-94 ° C

an η n 7 Rii

continued Table A

- 20 -

R1 R2 r3 (Y) m CH ^ 129 2 '~ (CHJ, CH., No 154-163 ° C / V = / C3H7 C3H7 2 6 3 3mmHg 130 ...... n'C5Hu Hl "^ 7. c

131 · * * - «2-0 HBr" m-137 * C

132 ......- «rQ-« "“;?: I47 * C

133 ..... i-C3 «7 Hl S ™ j?: I56oc k. p.

134 "" "KJ !, - no 139 ° C / 3mmHg i ie n ii it Γ · Η UT · P ·

135 C2H5 HI 157-158 ° C

i ie ii 1 “n-Γ H” Dec.

C5Hi; 1 C5Hi; 1 3 7 124-126 ° C

137 0, Cς C-Ης -CH, CH = CH, no 122 ° C / ^ ^ t 6nunHg k.p.

138 "-CH2C3CH" 132-13 3 ° C /

Gmmilg 800 0 7 65

continued Table A

X τ n '^ y ~ r1 r2 r3 (Y) m - 21 -

"CH, k D

already 3 λ. p.

r h c η '133-136 ° C / C2H5 L2H5 -CH-COOC2H5 none 3mmHg C00-i-C-jH- * 5 o 140 "" -CH <3 "n 1,4830 COO-i-C3H.

k. p.

14l "'·' · -CHnCOOCH," 144-153 ° C / 1 J 7mmHg k. P.

142 "" "-CH2COO-i-C3H." 117-134 ° C / 1 3mmHg -C-CH, k.p.

143 »·· ·· | j J" 130-134 ° C / O ImmHg -C-CH.CH, k.p.

144 - »·· II" 136-138 ° C / O ImmHg .. μ -C-γ y "sm.p.

145 "||> = / 68-70 ° C

O

".. .. -c-TVa" sm.p.

146 || 150-152 ° C

O

-C ^ fVcH ^ sm.p.

147 || 3 140-141eC

O

----- 0CH

1 «'" "-C-O" & 7.C

__J_ O___ o η η n 7 - 22 -

Xn '^ 3 ”R1 R2 R3 (Y) m

continued Table A

λ — λ -C-C1-Ci, 23 149 \ _y ^ C2H5 C2H5 II no lf 5540 -C-CH-SCH- 1 ςη "" "II Z ^ 150 JD 1,5640 -CCH-Si-C7H7 151" " "o" nD X »5521 152" "TH2S-0" "d4 M066 0 -CO 23 153" "" if ° "nD i <SB2 °

O

-cJD 23

154 "" "if S" nD 1f 594S

O

ch3 155 "" -C-CH = C <^ "nQ2 1.5508 0 3 ch3

i er ti η tl -C-C-C <m _19 1 C 1QC

156 (| | H nD 1,54 9 5 O CH3 -C-CH-OC-Ης, 157 "" "II ά 1 5 n11" "D 1,5240 -C-CH-OCH., ..

158 "" "II nj: u 1.5400

O You

80 0 0 7 65. - 23 -

continued Table A

ψ X

“0. R1 R2 R <*> "<

™ -CCH, CH, OC, H. , Q

159 O "C2HS C2H5» 9β6η nD ^ 5 ° 52 -CCHCH ^ 160 "II" nD ^ 5580

O

-CCC2.-, „„ 7Γ 3 .. sm.p.

161 ° II 73-74 ° C

O

-CCH ^ Br 162 "II 2" "d 1> 5624

O

-CCH-I "163" II "% 1> 5920

O

164 M "" II "= 79-82 ° C

O

165 f-C3H7 C3H7 -jjO-01 "" d3 1.5805

Xt =? / O ----- CÏNÖ ^

166 "" "" 115-116 ° C

_____O NQ2 ___ -C-O-CH- k.p.

167 C3H-C-H, I! 132-133 ° C / -C-OC-H. K.p.

168 - »" l | "148-149 ° C / O 2mmHg 80 0 0 7 65" - 24 -

continued Table A

X "'0- R1 R2 R3 <*)> λ-λ -COC ^ H ^ k.p.

169 f V_ C-H- C-Ης II J 'no 142-145 ° C / \ = / 2 5 ^ 3 0 0.75mmHg -CO-i-C, H- k.p.

170 "" "|| J '113-122 ° C / 0 0.25mmHg“ COC.Hq k.p.

171 »" "|| 141-144 ° C / 0.45mmHg

/ CH

172 "|| XCH, nD ^ 5543 0 -CSC2H ^ 21 173" "II" n * 1 1,5670 0 174 '"" Ό "nD5 ^ 5763 0 175" "" -CO-f) "n * 5 1 , 5675 _____o ^ ch3 ___ -CN 3 P176 "" "li XrH" 142-144 ° C / IJ 3 0.8mmHg _ XC2H5 Jc.p.

177 "η \ c H" 140 ° C / q 2tt5 0.6mmHg / C3H7 k.p.

178 "~ nNV h" 144-147 ° C / ”l3h7 0.5mmHg 300 0 7 65

continued Table A

- 25 - ft Χ "Λ R1 R2 R3 (V)"> α-CNHCH, _ "3 sin.p.

C2H5 C2H5 I * no 72-74 ° C

-CNHC-H- „.. π II 2 5 · <5ΓΠ · P ·

180 "11 69-70 ° C

0 -CNHC-, Η- ,, IB! - - - II 3 7 "" 5J 1.5418 0 -CNHC4Hg M m.p.

182 "" "II 66-68 ° C

0 ". CNHCMH / an.p.

183 "|| || \ = / 164-165eC

0 0 _ „-CNHCNH-fVci„ sn.p.

184 "l | II Λ = 3'148-150 ° C

0 0 10- „,. .. -CNH-O .. 'sn.p.

185 || N = / 105-107 ° C

0 186 ”" "i-6016 0 Cl 187 ..... 7HO" D * 1 · 5982 0 N'CH3 188 ”___0_ I · _ 800 0 7 65

continued Table A

Xn-0. R1 R2 R3 (Y) m - 26 - -CNHCH 13 189 / C2H5 C2H5 11 no nD 1f6101 -CNH-1-C ^ H-.

190 "" M II "nir 1,5888 S u 1Q1 ,, π» -CNH- / V) „sm.p.

III II -f 87-89 ° C

O

, Q9 «.1 n“ CNH— / H \ „sn.p.

192 II / 152-153 ° C

S

193 YHCH2-0 ”1,6200 s 194" "" -SG2CH3 "n21 1,5533 1QC It tl tt ΟΛ f U II Sm.p.

19: j bU2L2H5 76-77 ° C

196 "" -5Ο2 "0" "& 4« C

197 "-SOjQ-CH," S "giO2.c 199" "-SoQQ-Ci" * i121.c 800 0 7 65 -27 -

continued Table A

R1 R2 R3 (Y) ra 199 C2H5 C2H5 -S02 - ^^ r none ^ P; i45 „c

200. * "-S02CF3" 3102-103 ° C

201 ..... -S02CH2C1 ”S ^? 3rc -CNHCOCH- 702" "" II II J "sm, P *

zuz η π 138-139 ° C

-CNHCOC ^ H- -] rt} II II II II II ^ -5 II Sin. p.

Mp 112-113 ° C

-CNHCOC, H- m 204 "" "|| || J /" an.p.

£ 93-95 ° C

-CNHCO-i-C ^ H7 7 / -. Σ it ii ii II II ^ „an.p.

3 Q 113-115 ° C

"I, -CNHCO- / Λ" dec.

II II W 14 5-14 6 ° C

S O

«Η η n 7 65 i - 28 -

The kidney compounds of the invention can be prepared according to the reaction scheme a of the formula sheet. The reaction is carried out at room temperature up to 60 ° C in an organic solvent or without any solvent. As the solvent to be used can be mentioned benzene, toluene, xylene, chlorobenzene, tetralin, nitrobenzene, chloroform, carbon tetrachloride, dioxane, ethers and the like. The aluminum chloride complex of a benzamidine 10 of the formula sheet of the formula sheet thus obtained is decomposed with water or an inorganic acid and then treated with a strong alkaline agent to yield a benzamide group of the formula 8 of the formula sheet. As the inorganic acid, hydrochloric acid, sulfuric acid, nitric acid and the like can be used. The decomposition is preferably performed at room temperature to 50 ° C. As the strong alkaline agent, sodium hydroxide, potassium hydroxide and the like can be used, and the treatment therewith is preferably carried out below room temperature.

Furthermore, the benzamidine derivative of the formula 8 can also be prepared by reacting a Grignard reagent with a secondary amine in a solvent and then with a nitrile under heating, followed by decomposition of the product with ammonium chloride and then treatment with a strong alkaline agent.

A benzamidine derivative of the formula 9 of the 3 L formula sheet, wherein R represents the same substituents 3 as defined for R except a hydrogen atom, can be obtained by reacting the benzamidine derivative of the formula 8 with a compound of the 3 '3' formula R-Z, wherein R has the same meaning as defined above and Z represents a halogen atom such as a chlorine or bromine atom, an isocyanate group or an iso-thiocyanate group. The reaction can be carried out without any solvent or in an inert solvent such as ether, benzene, acetone, tetrahydrofuran, dioxane and the like, optionally in the presence of a base such as potassium carbonate, sodium carbonate, pyridine, 800 0 7 65 - 29 - triethylainine, sodium hydroxide , potassium hydroxide and the like, at room temperature up to 250 ° C.

When the benzamidine derivative of the formula 8 or 9 is treated with an acid, a salt of the formula 5 can be obtained. As the acid can be used hydrochloride, hydrogen bromide, hydrogen iodide, perchloric acid, nitric acid, mallonic acid, oxalic acid, picric acid, tartaric acid, benzenesulfonic acid, terephthalic acid, adipic acid, salicylic acid, formic acid, acetylsalicylic acid, cyclohexanecarboxylic acid, propionic acid, acrylic isoic acid , citric acid, alkyl benzene sulfonic acid, amino benzene sulfonic acid, dehydroacetic acid and the like. Therefore, Y in formula 5 represents the acid. The acid treatment can be carried out by dissolving the acid in a solvent such as water, ethers, dioxane, dimethyl sulfoxide, dimethylformamide, benzene, acetone, hexane, ethanol, methanol, isopropanol, tetrahydrofuran and the like, and then add benzamidine derivative to the solution at low temperature up to 100 ° C.

The method according to the invention is elucidated on the basis of the following exemplary embodiments.

Example I,

Preparation of Ν, Ν-diethylbenzamidine (compound No. 1).

After 14.3 g (0.1 mole) of powdered anhydrous aluminum chloride was added in small portions with cooling and stirring to a mixture of 10 g (0.097 mole) of benzonitrile and 9.5 g (0.128 mole) of diethylamine, the mixture was left react at about 50 ° C for 1.5 hours.

The reaction mixture was poured into 200 ml of ice water containing 4 ml of concentrated hydrochloric acid and then a solution prepared by dissolving 40 g (1 mol) of anhydrous sodium carbonate in 150 ml of water was gradually added thereto to make the mixture strongly basic. After stirring the mixture for 30 min.

it was extracted with ether. The extract was dried over anhydrous sodium sulfate and distilled to give 15.7 g of Ν, Ν-diethylbenzamidine as a pale yellow liquid.

800 0 7 65 - 30 -

Example II.

Preparation of N, N-diethylbenzamidine oxalate (compound No. 71).

After dissolving 2.1 g of oxalic acid in 30 ml of ethanol, 3.0 g of the N, N-diethylbenzamidine prepared in Example 1 was added dropwise thereto under cooling. The reaction mixture was left to stand overnight and then the ethanol was removed from the mixture to obtain crystals which were recrystallized from a mixture of ethanol and ether to give 4.0 g of Ν, Ν-diethylbenzamidine oxalate as colorless crystals. obtained.

Example III.

Preparation of N, N-di-n-propyl-4-methylbenzamidine 15: • (compound No. 26).

11.7 g (0.1 mol) p-tolu-nitrile and 12 g (0.12 mol) di-n-propylamine were dissolved in 50 ml benzene.

To the resulting solution, 16 g (0.11 mole) of powdered anhydrous aluminum chloride was added in small portions and the resulting mixture was further stirred for 3 hours at a temperature of no more than 60 ° C. After the reaction mixture was poured into 200 ml of ice water, 200 ml of a 20% aqueous solution of sodium carbonate was gradually added thereto to make the mixture strongly basic. After then stirring for 30 min, the mixture was extracted with two 100 ml portions of benzene. Then the benzene layer thus obtained was dried over anhydrous sodium sulfate and the benzene was removed by distillation. The residue was distilled under reduced pressure to obtain 16.5 g of the desired product as a pale yellow liquid.

Example IV.

Preparation of Ν, Ν-diethylbenzamidine adipate 35 (compound No. 73).

8.3 g (0.056 mol) of adipic acid were dissolved in 150 ml of ethanol. To the resulting solution, 10 g (0.056 mol) of the Ν, Ν-diethylbenzamidine prepared in Example 1 was added dropwise gradually at 80 ° C, to room temperature, at 80 ° C. The reaction mixture was allowed to stand in a refrigerator for 3 days and then the precipitated crystals were collected by filtration and then recrystallized from a mixture of ethanol and ether to yield 12.5 g of the desired product as colorless crystals.

Example V '.

Preparation of Ν, Ν-diethyl-N1-isopropylbenzamidine (Compound No. 104).

After a mixture of 3 g (0.017 mol) of N, N-diethylbenzamidine, prepared in Example I, and 8.7 g (0.051 mol) of isopropyl iodide was heated at 80 ° C for 1 hour and then cooled, it was mixture made strongly basic with a 25% aqueous solution of sodium 15 carbonate. After extraction with ether, the organic layer was dried over anhydrous sodium sulfate and then distilled to give 1.3 g of N, N-diethyl-N'-isopropylbenzamidine as a colorless liquid.

Example VI.

Preparation of Ν, Ν-diethyl-N1-ethoxycarbonylmethylbenzamide (Compound No. 110).

5.3 g (0.03 mol) of the Ν, Ν-diethylbenzamidine prepared in Example 1 were dissolved in 50 ml of ether. 5.1 g (0.03 mol) of ethyl bromoacetate were added dropwise to the resulting solution at room temperature with stirring. The mixture, which soon became cloudy and the temperature of which rose slightly, was refluxed for 2 hours with stirring. After the mixture was allowed to cool, a concentrated aqueous solution of sodium hydroxide was added thereto to make the mixture strongly basic. After the resulting mixture was extracted with ether, the ether layer was dried over anhydrous magnesium sulfate. Thereafter, the solvent was removed by distillation under reduced pressure and the resulting residue was distilled under reduced pressure to obtain 4.7 g of the desired product as a pale yellow liquid.

800 0 7 65 - 32 -

Example VII.

Preparation of N, N-diethyl-N'-methoxymethylbenzamidine (Compound No. 120).

5.3 g (0.03 mol) of the Ν, Ν-diethylbenzamidine prepared in Example 1 were dissolved in 50 ml of benzene.

When 2.5 g (0.032 mol) of methoxymethyl chloride was gradually added dropwise to the solution with stirring, the mixture soon became cloudy. The mixture was stirred as such at room temperature for 10 hours. After refluxing for 10 min.

the mixture was allowed to cool and then made strongly basic by adding a concentrated aqueous solution of sodium hydroxide. After extraction with benzene, the benzene layer thus obtained was dried over anhydrous magnesium sulfate and the solvent was removed by distillation under reduced pressure. The resulting residue was distilled under reduced pressure to obtain 1 g of the desired product as a colorless liquid.

20 Example VIII.

Preparation of NyN-diethyl-N1-allylbenzamidine (Compound No. 137).

A mixture of 5.0 g (0.0284 mol) Ν, Ν-diethylbenzamidine prepared in Example 1 and 5.2 g (0.0425 mol) allyl bromide was refluxed for 1.5 hours. After cooling, the mixture was made basic with 25% aqueous solution of sodium hydroxide and then extracted with ether. After the ether layer was dried over anhydrous sodium sulfate, it was subjected to distillation under reduced pressure to obtain 2.1 g of the desired product as a colorless liquid.

Example IX.

Preparation of N, N-diethyl-N'-bis (isopropoxycarbonyl) -35-methylbenzamidine (Compound No. 140).

5.3 g (0.03 mol) of the Ν, Ν-diethylbenzamidine, prepared in Example 1, 8 g (0.03 mol) diisopropyl bromalonalonate and 4 g (0.03 mol) anhydrous potassium carbonate were added to 100 ml of acetone and let the 800 0 7 65-33 mixture boil under reflux for 3 hours. After it had cooled, insolubles were removed by filtration and the acetone was distilled off under reduced pressure. The residue thus obtained was dissolved in benzene and washed with brine. After that, the benzene layer was dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The concentrated benzene solution thus obtained was subjected to column chromatography on silica gel, eluting first with benzene and then with a mixture of benzene and ethyl acetate (4: 1), whereby 2.1 g of the desired product were obtained as a pale yellow liquid.

Example X.

Preparation of Ν, Ν-diethyl-N1-methoxycarbonylbenzamidine (Compound No. 167).

5.0 g (0.028 mol) of the Ν, Ν-diethylbenzamidine prepared in Example 1 and 3.9 g (0.028 mol) of potassium carbonate were added to 200 ml of acetone. To the resulting mixture, 5.3 g (0.057 mol) of methyl chlorocarbonate was added dropwise under ice cooling. Then, after stirring for 2 hours under ice-cooling and standing overnight, the reaction mixture was filtered and the filtrate was evaporated and extracted with benzene. After treating the benzene layer successively with a dilute aqueous solution of sodium hydroxide, dilute hydrochloric acid and water in this order, it was subjected to distillation to yield 2.4 g of Ν, Ν-diethyl-N'-methoxycarbonylbenzamidine as a yellow liquid.

Example XI.

Preparation of Ν, Ν-diethyl-N'-phenylcarbamoylbenzamidine (compound No. 185).

5.3 g (0.03 mol) of the Ν, Ν-diethylbenzamidine prepared in Example 1 and 3.7 g (0.03 mol) of phenyl isocycanate were added to 80 ml of benzene and the mixture was stirred at room temperature for 3 hours .

After the reaction mixture was evaporated under reduced pressure to about 40 ml, n-hexane was gradually added thereto 800 0 7 65 - 34 - to obtain crude crystals, which were then recrystallized from a mixture of benzene and n-hexane to give 4, 8 g of N, N-diethyl-N'-phenyl-carbamoyl-benzamidine were obtained as colorless crystals in the form of fine grains.

Example XII,

Preparation of Ν, Ν-diethyl-N'-methylthiocarbamoylbenz-amidine (Compound No. 189).

5 g (0.0284 mol) of the Ν, Ν-diethylbenzamidine prepared in Example 1 were dissolved in dried benzene and 2.1 g (0.0284 mol) of methyl isothiocyanate were added dropwise thereto under ice-cooling. After the addition, the mixture was allowed to react for 30 min at room temperature with stirring and then it was heated at 40 ° C for 1 hour in a water bath. It was left overnight and then the benzene was removed by distillation and the resulting product was subjected to column chromatography on silica gel to isolate 5.2 g of the desired product as a pale yellow viscous oil.

Example XIII.

Preparation of Ν, Ν-diethyl-N'-trifluoromethanesulfonyl-benzamidine. • (connection no. 200).

5.3 g (0.03 mol) of the Ν, Ν-diethylbenzamidine prepared in Example 1 and 4.3 g (0.03 mol) anhydrous potassium carbonate were added to 50 ml of acetone. To the stirred mixture was gradually added dropwise a solution of 5 g (0.03 mole) of trifluoromethanesulfonyl chloride in a small amount of acetone under ice cooling and the mixture was stirred as such under ice cooling for 1 hour. The temperature of the mixture was then allowed to rise to room temperature and it was stirred overnight. After insoluble filtration, the acetone was removed from the filtrate under reduced pressure and the residue was dissolved in benzene. After the thus obtained benzene solution was washed with water and then dried over anhydrous magnesium sulfate, the solvent 800 0 7 65-35 was evaporated under reduced pressure. After recrystallization of the residue from a mixture of benzene and n-hexane, 3 g of the desired product were obtained as colorless crystals in the form of granules.

Example XIV.

Preparation of N, N-diethyl-N '- (ethoxycarbonylthiocarbamoyl) -benzamidine (Compound No. 203).

6.3 g (0.062 mol) of potassium rhodanate were added to 100 ml of anhydrous acetone. Then, 6.2 g (0.057 mol) of ethyl chlorocarbonate was added thereto at room temperature and the mixture was heated for 30 min. Then, after Ν, Ν-diethylbenzamidine prepared in Example I was added thereto under cooling with ice water, the mixture was stirred at room temperature for 4 hours. The reaction mixture was poured into 300 ml of ice water, followed by recrystallization of the precipitated crystals from ethanol, whereby 9.5 g of N, N-diethyl-N1- (ethoxycarbonylthiocarbamoyl) benzamidine were obtained as pale yellow crystals.

In another aspect of the invention there is provided a fungicidal composition containing as active ingredient a benzamidine derivative of any one of formulas 8, 9 or 5 as well as an agricultural acceptable carrier.

Among the compounds useful as active ingredients for the agricultural fungicidal composition of the invention, preference is given to the compounds of the formula wherein R and R each represent an elkyl group, in particular an ethyl group, 3 R represents a hydrogen atom or an alkyl group, such as an isopropyl group, an alkoxycarbonylmethyl group, an OC-alkoxycarbonylethyl group, an alkoxoymethyl group, a bis (alkoxycarbonyl) methyl group, a formyl group or a lower alkoxycarbonylthiocarbamoyl group and X represents a hydrogen atom or a halogen atom such as a chlorine, bromine , or salts thereof such as the terephthalate, adipate, salicylate, tartrate or hydrochloride.

When the benzamidine derivative of the invention is used as a fungicide, the compound 800 0 7 65 - 36 - can be formulated for use in the form of the compositions commonly used as a fungicide, for example dusting powders, granules, wettable powders, emulsifiable concentrates, in water soluble powders, liquid formulations and the like, together with an inert carrier.

As the inert carrier, any of the solid, liquid or gaseous carriers commonly used for herbicides may be mentioned, and may be, for example, tallow, glue, kaolin, diatomaceous earth, "white carbon", calcium carbonate, potassium chlorate, saltpetre, wood flour, starch , nitrocellulose, gum arabic, vinyl chloride, carbon dioxide, Freon, propane, butane and the like.

The fungicidal composition of the invention may optionally also be mixed with any preparation aid, for example, spreading agents, dispersants, emulsifying agents and the like, as is usually done in this technique.

In addition, the fungicidal composition according to the. The invention can also be mixed with herbicides, insecticides, other agricultural chemicals, fertilizers, for example urea, ammonium sulfate, ammonium phosphate, potassium fertilizers, soil conditioners and the like.

The above carriers and various auxiliaries may optionally be used alone or in combination therewith for desired purposes, taking into account the type of composition, the method of application and other factors.

For example, dusting powders usually contain 1-25 parts by weight of the active compound and the remainder is a solid carrier.

Wettable powder usually contains, for example, 25-90 parts by weight of the active compound and the remainder is a solid carrier and a dispersant and wetting agent, if desired, together with a protective colloidal agent, a thixotropic agent, an anti-foaming agent. and such.

Granules usually contain 1-35 parts by weight of 800-67-37 - the active compound and a main component of the remainder is a solid carrier. The active compound is homogeneously mixed with the solid support or adhered or adsorbed on the support surface and the size of a granule is about 0.2-1.5 mm.

Emulsifiable concentrates usually contain, for example, 5-50 parts by weight of the active compound and about 5-20 parts by weight of an emulsifying agent, the remainder being a liquid carrier, if desired, together with a corrosion inhibitor.

The fungicidal compositions according to the invention which can be formulated in different types of preparations as mentioned above, can be applied in a padi or high field in amounts of 15 1-5000 g, preferably 10-1000 g of the active ingredient per 10 are , for foliar spraying before or after hatching or soil watering or spraying on water for effective disease control.

Furthermore, the fungicidal compositions of the invention, when used for seed disinfection or coating, can effectively combat soil or seed infectious diseases by coating seeds in amounts of 0.1-2 wt%, preferably 0.2-0 , 5% by weight of the active ingredient, based on the weight of the seed.

The fungicidal composition according to the invention shows excellent effects in particular with respect to powdery mildew of various field crops even in smaller amounts, compared to commercially available fungicidal compositions.

In addition, the fungicidal composition according to the invention also has an excellent effect on such plant diseases as gray mold, anthracnose, rotting disease ("blast disease"), brown spots, bacterial soft rot, "bacterial leaf blight", screlotium disease and cancer (Valsa mali). Furthermore, the fungicidal composition according to the invention shows exceptionally low phytotoxicity against field crops as well as exceptionally low toxicity to humans and animals.

800 0 7 65 - 38 -

Examples of the preparation of fungicidal compositions according to the invention are given below. All parts are parts by weight unless otherwise indicated.

5 Preparation Example 1. Emulsifiable concentrates.

20 parts of Ν, Ν-diethylbenzamidine (Compound No. 1), 5 parts of Toxanone (trade name of a surfactant of Sanyo Kasei Kogyo K.K.) and 75 parts of xylene were homogeneously mixed to give 100 parts of emulsifiable concentrate.

Preparation example 2. Wettable powders.

20 parts N, N-di-n-butyl-2,5-dimethylbenzamidine (Compound No. 28), 1 part Demol EP powder (trade name of a surfactant from Kao-Atlas Co., Ltd.) 15 20 parts White carbon and 59 parts of talc were homogeneously mixed and powdered to obtain 100 parts of wettable powder.

Preparation example 3. Dusting powders.

2 parts of N, N-diethyl-p-chlorobenzamidine (Compound No. 48) and 98 parts of talc were mixed homogeneously to give 100 parts of dust.

Preparation Example 4. Granules or Tablets.

10 parts of N, N-tetramethylene-2-methylbenzamidine (compound No. 86), 15 parts of starch, 2 parts of bentonite 25 and 3 parts of sodium salt of lauryl alcohol sulfate were homogeneously mixed and powdered to give 100 parts of granules or tablets.

The effect of the agricultural fungicidal compositions according to the invention will now be elucidated on the basis of the following test examples. The numbers of the tested compounds correspond to those shown in Table A.

Trial example 1.

Effect on powdery mildew in cucumbers.

Cucumber seedlings (variety Sagamihanjirofushinari), each planted in a 6 cm diameter plastic pot, were used as host plants at the 17 day post sowing stage. Each host plant was treated with a dilute emulsifiable con 800 0 7 65-39 centrate, prepared according to Preparation Example 1 and containing 1000 ppm of each of the active compounds / by spraying in an amount of 20 ml per jar.

After air drying, each host plant was inoculated with Sphaerotheca fuliginea by homogeneously spraying its spore suspension. The spore suspension was previously prepared by brushing already infected cucumber leaves with a soft brush and dropping the microorganisms on a Petri-10 dish, and diluting the conidia with distilled water to such a concentration that 10 conidia were observed within the field of an optical microscope at a magnification of 150 times. The inoculated plants were stored in a glass greenhouse for 11 days and at the end of this period the number of affected spots on the first leaf was measured.

The percent effectiveness of each of the active compounds was calculated according to the equation: Average number of sites affected in treated groups

Percentage efficacy = 1 - x 100

Average number of sites affected in untreated groups 800 0 7 65 - 40 -

The results are shown in Table B.

TABLE B

Verb tested, efficacy (%) Phytotoxicity 1 100 none 2 95 "3 100 5 100 9 100 10 80 17 82 25 98 26 80 28 93 35 97 37 80 39 95 4 2 10 0 43 100 45 99 46 100 800 0 7 65

continued Table B

- 41 - 47 99 garfish 48 100 50 100 51 85 52 100 53 87

II

54 92

II

55 96 tl 57 94 58 100 59 100 60 100 61 100 63 100 64 100 65 100 66 100 67 100 68 100 69 100 70 100 71 100 72 100 73 100 74 100 75 100 76 100 77 100 78 100 79 100 80 100 81 100 83 98 84 98 Λ Λ Λ 85 100 "800 0 7 65 *

continued ^ Table B

- 42 - 87 100 Seen 88 100 89 80 90 100 91 100 92 100 93 100 94 100 95 100 96 100

"_ Λ II

97 100 98 100 99 100 100 100 101 95 10 2 99 103 100 104 100 105 94 106 100 107 100 108 100 109 85 110 100 112 100 114 98 115 96 116 92 117 100 118 100 120 89 122 85 123 80 124 91 800 0 7 65 - 43 - ê

Continue Table B

_> -— - - - - - - 126 82 none 127 100 128 95 129 100 130 90 131 87 132 100 133 84 134 89 135 80 136 100 143 100 144 88 145 72 146 92 147 100 148 100 149 100 150 81 151 84 152 75 153 100 154 94 155 87 156 85 157 100 158 100 159 94 160 100 161 100 162 92 163 83 164 100 165 86 80 0 0 7 65 - 44 -

Continued Table B

166 89 none 167 92 168 80 169 86 170 96 171 90, 172 100 173 100 174 100 176 82 177 80 178 85 179 78 180 80 181 84 183 96 184 100 185 100 186 94 188 82 189 86 190 95 191 100 192 100 193 93 194 100 195 100 200 75 203 100 204 98 205 95 206 90 800 0 7 65 - 45 -

continued table B

ak

Comparative Morestan. 89 no agent N-ethylbenzamidine 12 "Nn-propyl-benzamidine 7" N-isopropylbenzamine hydrochloride 0 "Nn-octyl leaves benzamidine 0 turned brown 10 N-decyl-N'-octyl-isobutane-amidine 75 none. N-benzyl-1'-octyl-isobutanamidine 81 11 * Commercially available 25% by weight wettable powder of S, S-6-methylquinoxaline-2,3-diyldithio-carbonate.

Trial example 2,

Effect on powdery mildew in cucumbers at low concentrations.

Tests were carried out according to the method described in Test Example 1, except that 40 ml of each of the dilute emulsifiable concentrates, prepared according to Preparation Example 1 and containing 50 ppm, 25 ppm or 12.5 ppm of each of the active compounds, was sprayed per group containing 10 seedlings.

The results are shown in Table C.

Λ Λ Λ Λ _ λ- Table C.

800 0 7 65 * - 46 -

TABLE C

"" "Concentration of Active-

Tested Verb, Active Compound (%) Ft Toxicity 50 100 None 1 25 99 12.5 95 50 100 43 25 95 12.5 87 50 97 67 25 93 12.5 90 50 100 78 25 95 12.5 94 50 100 164 25 93 12.5 87 50 90 172 25 76 12.5 61 50 69

Morestan 25 54 12.5 32 80 0 0 7 65 - 47 -

Test example 3.

Effect on powdery mildew in tobacco.

Tobacco seedlings (variety MC-1), each planted in an unglazed pot with a diameter of 12 cm, were used as gas bud plants at the stage of about 2 months after sowing. Each host peptide was inoculated with Erysiphe cichoracearum by spraying its spore suspension with a small glass sprayer.

The spore suspension was previously prepared by diluting the conidia with distilled water to such a concentration that 10 conidia were observed within the field of an optical microscope at 150 times magnification.

Two days or five days after inoculation, each host pigment was treated with a dilute emulsifiable concentrate prepared according to Test Example 1 and containing each of the active ingredients at a predetermined concentration by carefully spraying on the leaves. The plants were kept at 25 ° C in an air-conditioned greenhouse until the disease started to occur.

After the onset of the disease, the number of affected spots on the leaves was counted and the percentage efficacy was calculated in the same manner as described in Test Example 1. The results are shown in Table D. The average number of affected spots in untreated groups was 522.

Table D.

80 0 0 7 65 '- 48 -

TABLE D

Work seeding (%)

Investigated Concentration - -rr "-; - Fvi * ni-nvi compound of active 2 days after 5 days after specificity treatment treatment treatment f 200 100 100 none 1 100 97 95 50 96 87 200 100 100 46 100 100 97 50 95 89 200 100 100 67 100 98 98 50 74 71 200 100 100 78 100 89 90 50 83 76 200 100 100 164 100 91 88 50 89 79 200 100 100 172 100 95 91 50 92 89 200 100 99

Topsin-M 100 75 69 50 45 30 * Commercially available 50% by weight wettable powder of 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene 800 0 7 65 - 49 -

Test example 4.

Effect on gray mold in cucumbers.

Cucumber seedlings (Sagamihanjiro-fushinari variety), each planted in a plastic pot with a cross-section of 6 cm, were used as host plants at the 2-week post-sowing stage. Each host plant was treated with a dilute wettable powder prepared according to Preparation Example 2 and containing 1000 ppm of each of the active compounds by spraying in an amount of 20 ml per pot.

After air drying, each host plant was inoculated with Botrytis cinerea by spraying its suspension. The suspension was previously prepared by shaking the microorganism for 3 days in a yeast glucose medium, pulverizing with a homogenizer and diluting to a concentration such that the absorbance at 610pa was about 1.1 when measured with a spectrophotometer.

The host plants were stored at 20 ° C for 3 days in an inoculation chamber and the number of adapted plants in different degrees (n1 ~ n ^) was determined according to the following evaluation standard: 0: no infection observed (number of plants; n1) 25 1: few dip-like lesions observed "" n2 2; many immersion-like lesions observed, but no major lesions observed. "" n ^ 3: major lesions observed at less than approx.

1/5 of the total leaf area "" n4 35 4; large affected spots observed at approximately 1 / 4-1 / 5 of the total leaf area "" n ^ 5: large affected spots observed at approximately 1 / 2-1 / 4 ° of the total leaf area "" n ^ 80 0 0 7 65 - 50 - 6: large affected spots (number of plants: n7) observed on more than about 1/2 of the total leaf area 5 The percentage activity of each of the active compounds was calculated according to the equation: percentage = {i - ^ traded groups (0 x ^ + 1 x 1¾ + efficacy untreated 1st group. (0 x ^ + 1 x + 2 xn, + 3 xn, + 4xnr + 5xn, + 6xil), _3_i-Ë - 2 - ± 1 x 100 10 2 xn ^ + 3 x + 4 xn ^ + 5 x ng + 6 xn ^)

The results are shown in Table E.

Table E.

800 0 7 65 - 51 -

TABLE E

Examined verb. Activity (%) Fatotoxicity l 100 9a

II

3 X 95

II

4 80 it 8 85 10 "Ü 12 100 14 85

II

28 93 90 100 165 89 π 166 92 ”174 85 175 78" 186 90 194 75 ”195 96 * n <"

Difolatan 76 * Commercially available 80% wettable powder of N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide.

80 0 0 7 65 - 52 -

Test example 5.

Effect on anthracnose in cucumbers.

Cucumber seedlings (variety Sagamihanjiro-fushinari), each planted in a 6 cm diameter plastic pot, were used as host plants at the 16 day post sowing stage. Each host plant was treated with a dilute emulsifiable concentrate or wettable powder prepared according to resp. preparation example 1 or 2 and containing 1000 ppm of 10 of the active compounds each, by spraying in an amount of 20 ml per jar.

After air drying, each host plant was inoculated with Colletotrichumlagenarium by homogeneously spraying its spore suspension. The spore-suspension was previously prepared by culturing spores on a medium of sweet corn meal and diluting it to such a concentration that about 200 spores were observed within the field of an optical microscope at 150 times magnification.

After being allowed to stand at 27 ° C and 100% relative humidity for 1 day in a room, the host plants were transferred to a greenhouse and after 4 days the number of affected spots on the first leaf was measured. The percent effectiveness of each of the 25 active compounds was calculated according to the same calculation as described in Test Example 1 and the results are shown in Table F.

TABLE F

800 0 7 65 - 53 -

TABLE F

Researched Verb * Tferkzaanüeid (S) Phytotoxicity 3 100 none 5 10 100 16 90 ”56 95 85 100 86 95 10 90 100 101 96>“ 102 92 ”“ 103 98 104 100 15 137 93 138 80 139 90 ”14 0 85

Maneb Dithane * 93 * Commercially available 70% wettable powder of manganese ethylene bis dithiocarbamate.

** Formulation: emulsifiable concentrates of compounds Nos. 3, 10, 16, 56, 85, 86 and 90; wettable powders of compounds Nos. 101 to 104 and 137 to 140.

Test example 6,

Effect on bacterial leaf blight in rice plants.

Rice seeds (Nihonbare variety) were sown, 30 in each pot in a series of plastic pots with a diameter of 6 cm and grown in a glass greenhouse to the 5.5-6.5 leaf stage. Granules prepared according to preparation example 4 were applied by immersion in an amount of 15 mg per jar. After application 80 0 0 7 65 - 54 - the host plants were kept in the glass greenhouse for 2 days to allow the active compounds to absorb from the underground parts. Each host plant was inoculated with Xanthomonas oryzae 5 by two-needle needle prick inoculation into the top two leaves, avoiding the veins. The microorganism was previously obtained by shaking culture at 28 ° C for 48 hours in a Suwa liquid medium and at such a concentration

m Q

brought the number of ant organisms to 10 'per ml. The inoculated plants were kept in the glass greenhouse for 2 weeks and the length of the affected spots on the leaves was measured in order to calculate the number of leaves (n ^ -n ^) in different degrees of attack according to the following evaluation standard: 0 : No infection detected (number of leaves: n ^) 1: Slight infection detected "" ^ 2: Affected spots less than 20 cm observed "" n ^ 3: Affected spots less than 2 cm detected "" n ^ 4: affected spots less than 5 cm observed "" n ^ 25 5: affected spots less than 10 cm observed "" ng 6: affected spots greater than 10 cm observed "" n ^

The percentage activity of each of the active compounds was calculated, based on the above observation, according to the equation: 800 0 7 65 - 55 - treated groups (0. x ^ + 1 x n2 + percentage activity = yl - «, xn, + 1 x ^ +

2 x n3 + 3 x n4 + 4 x n5 + 5 x n6 + 6 x n7) χ l0Q

2 x n3 + 3 x n4 + 4 x n5 + 5 x n6 + 6 x n?)

The results are shown in Table G.

TABLE G

Examined verb. Efficacy (%) Phytotoxicity 31 76 none 47 '73 66 78 85 75 86 100 87 100 88 96 89 83 90 87 101 74 102 82 103 100 105 87 80 0 0 7 65 f - 56 -

continued Table G

HI 69 9a

_ _ II

112 95 116 79 117 83 119 72 121 76 157 100 161 70 162 96 163 95 167 85 168 89 169 100 171 79 172 82 175 100 179 75 180 68 181 86 182 79 183 75 184 83 190 96 194 98 195 100 198 88 199 92

Phenezine * 76 * Commercially available 10% wettable powder of phenazine 5-oxide 8 0 0 0 7 65 - 57 -

Test example 7.

Effect on bacterial soft rot in Chinese cabbage.

Chinese cabbage seedlings (variety Nozaki no. 2) grown in 6 cm diameter plastic pots at 25 ° C in an ari-conditioned greenhouse, were used as host plants at the 18 day post sowing stage. Each host plant was treated with a dilute wettable powder prepared according to Preparation Example 2 and containing 1000 ppm of each of the active compounds by spraying at 20 ml per jar. The plant was then incubated "with Erwinia aroideae E-7105 by spraying.

The microorganism was previously obtained by shaking culture at 28 ° C for 24 hours in a * 5 Suwa liquid medium and the diluted medium, containing the microorganism at such a concentration as to cause an appropriate infection, and carborundum (particle size 50 jam) were pre-mixed for spraying.

The inoculated host plants were kept at 28 ° C for 3 days in an inoculation chamber and the degree of infestation was observed to determine the infestation index in accordance with the following evaluation standard: 25

Evaluation standard of degree Infestation index of infestation_

No infection detected 0

Minor infection observed 1

Minor affected area observed 2 2 ° Affected area observed from approximately 1/4 of total area 3

Affected surface observed from approximately 1/3 of total surface 4

Affected surface observed from 35 approximately 1/2 of total surface 5

Whole plant infected 6 80 0 0 7 65 - 58 -

Based on the study, the percentage efficacy of each of the active compounds was calculated according to the equation:

Degree of infestation in treated groups

Employment rate percentage = (1 -) x 100

Degree of impairment in untreated groups

In the above equation, the extent of attack was calculated with the following equation, i.e., the percent value obtained by dividing the sum of the damage index of 10 trials by 60, since each trial was conducted in a series of 10 trials.

Scan of the infection index of

Degree of damage = Mproev®--M

60

The results are shown in Table H.

TABLE H

Examined verb. Efficacy (%) Eytotoxicity 11 75 none 55 82 57 90 65 65 85 76 88 93 90 100

Agrept * 75 "* Commercially available 25% wettable streptmycin sulfate powder (20% as Streptmycin) 800 0 7 65 - 59 -

Test example 8.

Effect against rice withering ("rice blast").

Rice seeds (variety Nohrin no. 20) were sown in pots with a diameter of 6 cm. and grown 5 to the 50% developmental stage of the fourth leaves.

20 ml each per jar of a dilute wettable powder prepared according to Preparation Example 2 and containing 1000 ppm of each of the active compounds were sprayed onto the leaves. After air drying, the host plant was inoculated with Piricularia oryzae by homogeneously spraying its spore suspension in an inoculation chamber. The microorganism was pre-cultured at 27 ° C for 7-10 days on a rice bran medium (3 g rice husk, 0.01 g powdered malt extract, 0.2 g glucose, 0.05 g soluble starch, 5 ml water).

The host plants were kept at 27 ° C at over 95% relative humidity for 2 days and then stored in a greenhouse for another 4 days.

The number of affected sites was calculated and the percent activity for each of the active compounds was calculated by the same method as described in Test Example 1. The results are shown in Table J.

25

Table J

800 0 7 65 - 60 -

TABLE J

Examined verb. Efficacy (%) Iytotoxicity 103 100 none 107 96 '5 113 93 114 86 115 88 125 100 127 100 10 128 93 129 96 "133 100 134 96 161 95 15 163 100 165 86 193 89 197 96 198 100 20 199 72 200 80 201 75 -----

Test example 9.

25 Effect on brown spots in rice plants.

Rice seeds (Nihonbare variety) were sown, 10 per pot, in 6 cm diameter plastic pots and grown to the 4.0 to 4.5 leaf stage. Each host plant was treated with a dilute wettable 3Q powder or emulsifiable concentrate, each prepared according to resp. preparation example 2 or 1, and containing 500 ppm of an active compound, in an amount of 20 ml per jar. After air drying, the host plants were inoculated with Cochliobolus miyabeanus grown in a rice straw extract medium at 28 ° C for 10 days and brought to a concentration such that 10-15 conidia 800 0 7 65-61 were observed within the field of an optical microscope with a magnification of 150 times. The inoculated plants were kept at 27 ° C at over 95% relative humidity in an inoculation chamber for 2 days.

The number of affected spots that appeared on the top two leaves was measured and the activity of each of the active compounds was calculated by the same method as described in Test Example 1. The results are shown in Table K.

10 TABLE K

Verbs examined Efficacy (%) Phytotoxicity 113 100 none 114 93 115 97! 15 116 99 137 85 138 77 139 87 140 80 20 145 86 152 82 158 100 161 80 162 93 25 163 100 164 95 172 89 173 91 174 87 30 189 89 190 82 193 100 ___ 800 0 7 65 - 62 - *

Formulation: wettable powders of compounds Nos. 113 to 116 and 137 to 140; emulsifiable concentrates of compounds Nos. 145, 152, 158, 161 to 164, 172 to 174, 189, 190 and 193.

Test example 10.

Effect on sheath blight11 in rice plants.

Rice seeds (Nihonbare variety), 10 per pot, were sown in pots of 6 cm diameter and 10 grown to the 7-8 leaf stage. 20 ml per jar of a dilute wettable powder prepared according to preparation example 2 and containing 500 ppm of an active compound was sprayed on the host plants. After air drying, each host plant was inoculated with the Pellicularia sasakii by the microorganism grown for 14 days on a rice bran medium, placed on the potting soil and placed in an inoculation chamber within a greenhouse. 7-10 days after the inoculation, the length of the affected spots that appeared on the stem of rice plants was measured and the damage index was determined in accordance with the following evaluations:

Infection evaluation standard Infestation index No infection observed 0 (number of plants: n ^ 25 Minor infection observed 1 "” ^

Affected spots less than 1 cm were observed 2 "11 n ^

Affected spots less than 2 cm observed 3 "" n4 30 Affected spots less than 5 cm detected 4 "" n ^

Affected spots less than 10 cm were observed 5 "" n ^

Affected spots over 35 cm observed 6 "" n ^ 800 0 7 65 - 63 -

Based on the observation, the percentage efficacy of each of the active compounds was calculated according to the equation: treated groups (0 x ηχ + 1 x +

Percentage of work- = | 1 - —- “_, τ„ n I

5 non-treatment groups (0 x ηχ + 1 x n2 + 2 x n3 + 3 x n4 + 4 x n5 + 5 x n6 + 6 xn?) _______ ^ x 100 2 x n3 + 3 x n4 + 4 x n5 + 5 x n6 + 6 x n7)

The results are shown in Table L.

TABLE L

] _q Examined verb. Efficacy Phytotoxicity 145 99 none 146 94 ", 147 85 161 91 15 162 80 163 83 164 95 800 0 7 65 - 64 -

Test example 11.

Effect on powdery mildew in barley.

Barley seeds (Kuromugi variety) were sown, 10 per pot, in 15 cm diameter unglazed pots and grown until sufficient development of the first leaf in a glass greenhouse for 7 days at 20 to 25 ° C. The emulsifiable concentrate containing N, N-diethylbenzamidine (Compound No. 1), which was prepared according to Preparation Example 1, was diluted to a prescribed concentration and sprayed on the leaves of the host plants at 20 ml per pot . After air drying, the first leaf of each of the treated host plants was inoculated with the spores of Srysiphe graminis H-14 by spraying. The inoculated plant was kept in a glass greenhouse at 20-25 ° C for 7 days and at the end of the period the degree of attack was measured. The results are shown in Table M.

Test example 12.

- - -

Effect on crown rust ("crown rust11") in oats.

Oat seeds (variety Zenshin) were sown, 20 per pot, in 15 cm diameter unglazed pots and grown to develop the second leaf in a glass greenhouse for 7 days at 20 to 25 o 25 C. The emulsifiable concentrate, containing N, N-diethylbenzamidine (compound, no. 1), which was prepared according to preparation example 1, was diluted with water to a predetermined concentration and sprayed on the leaves of the host plants in an amount of 20 ml per pot.

After air drying, the host plant was inoculated with the spores of Puccinia coronata by spraying a suspension thereof and then placed in a wet room at 23 ° C for 24 hours and then grown in a glass greenhouse at 20 ° C. 25 C.

20 days after the inoculation, the number of affected spots was counted and the extent of the damage was then calculated.

The results are shown in Table M.

800 0 7 65 - 65 -

Test example 13.

Effect on black rust ("black rust") in chrysanthemum.

Chrysanthemums (variety Ryazanshimpu), grown in 15 cm diameter unglazed pots, were used as host plants. The emulsifiable concentrate containing Ν, Ν-diethylbenzamidine (Compound No. 1) prepared according to Preparation Example 1 was diluted with water to a predetermined concentration and sprayed onto the host plants in an amount of 50 ml per pot, and then sprayed twice more at 7-day intervals. The host plants thus treated were naturally inoculated by placing affected plants infected with Puccinia chrysanthemi around the treated host plants. The extent of the infection was measured a month later. The results are shown in Table M.

TABLE M.

Concentration of Degree of impairment of active compound. Sample sample. Trial example.

. . (ppm) ._ 12 12 1000 1000 1.6 0 500 0 4.7 11.4 200 0 36.0 26.7 25 untreated groups 100 100 100

Conclusions.

800 0 7 65

Claims (12)

Novel benzamidine derivatives, characterized in that they have the formula 1 of the formula sheet, wherein X represents a lower alkyl group, a halogen atom or a methoxy or dimethylamino group, n has the 1 2 5 meaning 0, 1, 2 or 3, R and R are the same or different and each represents an alkyl, alkenyl, cycloalkylic phenyl group or, together with the nitrogen atom to which they are attached, form a saturated 5-7 membered alicyclic group which may contain an oxygen atom as a member of the ring next to the nitrogen atom and may be substituted with one or two methyl groups, and R represents a hydrogen atom or a straight or branched chain alkyl, alkenyl or alkynyl group, a chlorine substituted or unsubstituted chlorine, a cyano, Cyanoalkyl, alkoxycarbonylmethyl, & -alkoxycarbonylethyl, alkoxymethyl or bis (alkoxycarbonyl) methyl group, a phenoxyethyl group or a phenoxyethyl group substituted by an alkyl or alkoxy group, a group having the 4 f formula 2 (wherein R represents a hydrogen-20 atom or a lower alkyl group, a halogen-substituted methyl group, a lower alkoxy, lower alkoxyalkyl, lower alkenyl, lower alkylthiomethyl, furyl, thienyl, lower alkylthio or phenylthiomethyl group, a phenoxy-group, whether or not substituted by a methyl group, or a phenyl group, whether or not substituted by a halogen atom or a methyl, methoxy or nitro group), a group of the formula 3 of the formula sheet 5 6 (wherein R and R may be the same or different and each represents a hydrogen atom or a lower alkyl or cyclohexyl group, an anilinocarbonyl group, optionally halogen-substituted, or a phenyl group optionally substituted by a halogen atom or a methyl group), a group having formula 4 of the formula sheet (wherein R represents a lower alkyl, cyclohexyl, benzyl, lower alkoxycarbonyl or phenoxycarbonyl group), 8 or a group of the formula -SO 2 -R (wherein R represents a lower 80 0 0 7 65-67 -alkyl, trifluoromethyl or chloromethyl group or a phenyl group substituted or not by a halogen atom or a methyl group), or a salt thereof. 2. Compounds according to claim 1, characterized in that the lower alkyl group represented by X has 1 or 1 or 2 carbon atoms, that the alkyl, alkynyl and cycloalkyl groups represented by R or R represent 1, 5, 3 or 4 and 5 or 6 carbon atoms that the 5-7 membered saturated alicyclic group formed by R and R together with the nitrogen atom has a 1-pyrro-lidynyl, 1-piperidyl, 2-methyl-1-piperidyl, 2,2 6-dimethylpiperidyl or hexahydroazepinyl group is the straight or branched chain alkyl, alkenyl, alkynyl, cyanoalkyl, alkoxycarbonylmethyl, alkoxy-15-carbonylethyl, alkoxymethyl, bis (alkoxycarbonyl) methyl and R1 represented by R1 substituted phenoxyethyl groups have 1-13, 3 or 4, 3 or 4, 2 or 3, 3-6, 4-6, 2-5, 5-11 and 4 9 or 10 carbon atoms, respectively, that the lower alkyl represented by R lower alkoxy, lower alkoxyalkyl, lower alkenyl, lower alkylthiomethyl and lower alkylthio groups 1-3, 1-4, 2-4, 2-4, 2-5 and 1-4 5 respectively 6 have carbon atoms, that the lower alkyl group represented by R or R has 1-4 carbon atoms, that the lower alkyl and lower alkoxycarbonyl groups represented by 7 R have respectively 1-4 and 2-5 carbon atoms, and that Q represents the low represented by R alkyl group has 1 or 2 carbon atoms. 800 0 7 65 Process for preparing a benzamidine derivative of the formula 1, wherein X represents a lower alkyl group, a halogen atom or a methoxy or dimethylamino group 1 2, n has the meaning 0, 1, 2 or 3, R and R may be the same or different and each represents an alkyl, alkenyl, cycloalkyl or phenyl group or, together with the nitrogen atom to which they are attached, may form a saturated 5-7 membered alicyclic group which may contain an oxygen atom as a member of the ring next to the nitrogen atom or it may be substituted with one or two methyl groups, and R represents a -68- hydrogen atom or a straight or branched chain alkyl, alkenyl or alkynyl group, optionally by chlorine substituted benzyl group, a cyano, cyanoalkyl, alkoxycarbonylmethyl, alkoxycarbonylethyl, alkoxymethyl or bis (alkoxycarbonyl) methyl group, a phenoxyethyl group or a phenoxyethyl group substituted by an alkyl or alkoxy group, a call Formula 4 (wherein R represents a hydrogen atom or a lower alkyl group, a halogen-substituted methyl group, a lower alkoxy, age alkoxyalkyl, lower alkenyl, lower alkylthiomethyl, furyl, thienyl, lower alkylthio or phenylthiomethyl group, a phenoxy group, whether or not substituted by a methyl group, or a phenyl group, whether or not substituted by a halogen atom or a methyl, methoxy or nitro group), C g a group of the formula 3, (wherein R and R may be the same or different and each represent a hydrogen atom or a lower alkyl or cyclohexyl group, an halo-substituted anilinocarbonyl group or a halo or methyl-substituted phenyl growth group, a group with the form 7 mule 4 (wherein R represents a lower alkyl, cyclohexyl, benzyl, lower alkoxycarbonyl or phenoxycarbonyl group), 8 or a group of the formula -SC ^ -R (wherein R represents a lower alkyl, trifluoromethyl - chloromethyl or a phenyl group substituted or not substituted by a halogen atom or a methyl group), or a salt thereof, characterized in that a nitrile of the formula 6 of the formula sheet, wherein X and n have the same meaning as defined above, reacts 12 12 with a secondary amine RR NH, wherein R and R have the same meanings as defined above, in the presence of aluminum chloride to form a complex of a benzamidine and the aluminum chloride of formula 7 of the formula sheet , then decomposes the complex thus formed with water or an inorganic acid, then the product is treated with a strong basic agent to form a benzamidine compound of the 1 2 formula 8 of the formula sheet, wherein X, n, R and R 800 0 7 65, f - 69 - have the same meanings as defined above, and then react the benzamidine thus formed 3 '3 1 with a compound R-Z, wherein R is the same represents the substituents 3 as defined with respect to R 5 in addition to the hydrogen atom and Z represents a halogen atom or an isocyanate or isothiocyanate group, to form a benzamidine compound of the formula 9 12 3 'of the formula sheet, wherein X, n, R R and R have the same meanings as defined above, and further optionally treat the benzamidine compounds thus obtained with an acid to form a salt thereof. 4. Process according to claim 3, characterized in that the reaction of the nitrile with the secondary amine is carried out at room temperature up to 60 ° C in an organic solvent or without any solvent. 5. Process according to claim 3 or 4, characterized in that the complex of formula 7 is decomposed by hydrochloric, sulfuric or nitric acid at room temperature up to 50 ° C and the treatment with a strong basic agent is carried out with anhydrous sodium carbonate or anhydrous potassium carbonate below room temperature. 6. Process according to any one of claims 3-5, characterized in that the reaction of the 3 'benzamidine of the formula 8 with the compound R 2 is carried out in the presence of a base at room temperature up to 250 ° C. A fungicidal composition containing as active ingredient a benzamidine derivative of the formula 1, wherein X represents a lower alkyl group, a halogen atom or a methoxy or dimethylamino group, n has the meaning 1 2 0, 1, 2 or 3, R and R may be the same or different and each represent an alkyl, alkenyl, cycloalkyl or phenyl group, or together with the nitrogen atom 800 0 7 65 - 70 - to which they are attached, may form a saturated 5-7 membered alicyclic group may contain an oxygen atom as a member of the ring in addition to the nitrogen atom or may be substituted by one or two methyl 3-5 groups and R represents a hydrogen atom or a straight or branched chain alkyl, alkenyl or alkynyl group, whether or not by chlorine substituted benzyl group, a cyano, cyanoalkyl, alkoxycarbonylmethyl, 4l, -alkoxy-carbonylethyl, alkoxymethyl or bis (alkoxycarbonyl) -10 methyl group, a phenoxyethyl group or an alkoxy-substituted alkoxy group phenoxyethyl group, a 4 group of formula 2 (wherein R represents a hydrogen atom or a lower alkyl group, a halogen-substituted methyl group, a lower alkoxy, lower alkoxyalkyl, lower alkenyl, lower alkylthiomethyl, furyl, thienyl, lower alkylthio or phenylthiomethyl group, a phenoxy group, whether or not substituted by a methyl group, or a 5 6 20 phenyl group, whether or not substituted by a halogen atom or a methyl, methoxy or nitro group), a group of the formula 3 (wherein R and R may be the same or different and each represent a hydrogen atom or a lower alkyl or cyclohexyl group, an halo-substituted anilino-carbonyl group or a halo-substituted or unsubstituted phenyl group), a 7 group of the formula 4 (wherein R represents a lower alkyl, cycloalkyl, benzyl, lower alkoxycarbonyl or phenoxycarbonyl-O group), or a group of the formula -S09-R 8 ^ (wherein R ee n represents a lower alkyl, trifluoromethyl or chloromethyl group or a phenyl group substituted or not substituted by a halogen atom or a methyl group), or a salt thereof, together with a carrier suitable for use as an agricultural fungicide. A fungicidal composition according to claim 7, characterized in that in the active compound present therein the lower alkyl group represented by X has 1 or 2 carbon atoms, the alkyl, alkenyl and cycloalkyl groups represented by R or R represent 80 ° C 0 7 65 - 71 - also have 1-5, 3 or 4 and 5 or 6 carbon atoms, 1 2 the 5-7 membered saturated alicyclic group represented by R and R together with the nitrogen atom has a 1-pyrrolidynyl, 1-piperidyl -, 2-methyl-1-piperidyl, 5 2, β-dimethyl-1-piperidyl or hexahydroazepinyl group, 3 is the straight or branched chain alkyl, alkenyl, alkynyl, cyanoalkyl, alkoxycarbonylmethyl, represented by R -alkoxycarbonylethyl, alkoxymethyl, bis (alkoxy-carbonyl) methyl or substituted phenoxyethyl group 10 1-13, 3 or 4, 3 or 4, 2 or 3, 3-6, 4-6, 4 2- 5, 5- respectively 11 and 9 or 10 carbon atoms have the lower alkyl, lower alkoxy, lower alkoxylalkyl, lower alkenyl, lower alkylthiomethyl or lower alkyl represented by R hio group have 1-3, 1-4, 2-4, 2-4, 2-5 and 1-4 5 6 15 carbon atoms, the 7 lower alkyl group represented by R or R has 1-4 carbon atoms, the by R represented lower alkyl or lower alkoxycarbonyl group has 1-4 and 2-5 carbon atoms, respectively, and the 8 lower alkyl represented by R has 1 or 2 carbon atoms. 9. A fungicidal composition according to claim 7, characterized in that, in the active compound R and R contained therein, each represents an alkyl group, R represents a hydrogen atom or an alkyl, alkoxycarbonylmethyl, CC-alkoxycarbonyl ethyl, alkoxy methyl, bis (alkoxycarbonyl) methyl, formyl or lower alkoxythiocarbamoyl group and X is optionally a halogen atom. 10. A fungicidal composition according to claim 9, 12, characterized in that R and R each represent a 3 ethyl group, R represents a hydrogen atom or an isopropyl group and X is optionally a halogen atom. 11. A fungicidal composition according to any one of claims 7,8 or 9, characterized in that the compound contained therein is a salt selected from a terephthalate, adipate, salicylate, tartrate and 800 0 7 65-12. hydrochloride. A fungicidal composition according to claim 9 or 10, characterized in that the benzamidine derivative Ν, Ν-diethylbenzamidine, N, N-diethylbenzamidine-5 salicylate, Ν, diet-diethylbenzamidine adipate, N, N-diethyl-N'- formylbenzamidine, N, N-diethyl-N1-isopropylbenzamidine, N, N-diethyl-N1-ethoxycarbonylmethylbenzamidine, N, N-diethyl-N1-ethoxycarbonylthiocarbamoylbenzamidine, N, N-diethyl-N1-bis (ethoxycarbidine) 10 is N, N-di-n-propyl-N'-methyl-o-methylbenzamidine or N, N-diethyl-o-chlorobenzamidine. 800 0 7 65